Treatment of hydrocarbons



Patented May 28, 1940 i A more]; STATES TREATMENT OF HYDROCARBONS Jacque C. Morrell, Chicago, 111., assignor to Universal OilProducts Company, Chicago, 11]., a corporation of Delaware No Drawing. Application December 30, 1937, Serial No. 182,519

12 Claims. This application is a continuation-in-part of my co-pending application, Serial No. 32,638, filed July 22, 1935.

This invention relates particularly to the treat- 5 ment of parafiin hydrocarbons which are gaseous at ordinary temperatures and pressures and particularly propane and thebutanes, though in its general application it may include the treatment of ordinarily liquid paraffin hydrocarbons, as well 10 as naphthenes or cyclc-paraffin hydrocarbons.

In a more specific sense the invention is concerned with a novel process for. alkylating 3 and 4 carbon atom parafiln hydrocarbons with olefins which are normally gaseous to produce saturated hydrocarbons of higher molecular weight which can be utilized as constituents of motor fuel for automobile and aeroplane engines.

There is a very large production of fixed gases in connection with the production and refining Q of petroleum. Large amounts of parafiinic gases occur as natural gas and well or casing-head gases and further quantities are produced incidental to the cracmngof the heavier portions of v petroleums with the principal object of producfling gasoline. Petroleum gases are as a rule utilized only as fuel and from the standpoint of the oil refiner who is primarily concerned with the manufacture of gasoline and lubricating oils these gases are mainly considered as waste'mal0 terial, so that considerable experimentation has been conducted to find methods for converting them into liquid products with practical efllciency. The utilization of these gaseous materials. has

been attempted by employing straight thermal 85 treatment without catalysts, whichmethods in.-

volve ordinarily relatively higher temperatures and pressures than those employed in oil crack ing operations and by-catalyticprocesses which as a rule operate under less severe conditions. q The present process is related to the latter types of processes and the catalytic materials specified may also be employed in reactions involving thealkylation of normally liquid paraflins ornaphthenes when conditions are modified to take into 45 account the reactivities of the various. hydrol carbons.

In one specific embodiment the present inven- Y used in conjunction with hydrochloric acid.

'tion'comprises the alkylation of parafiin hydrocarbons with normally gaseous olefin hydrocar 50 hour at temperatures within'the approximate range-of 50 to +20 C. and preferably below 0 C. with catalysts comprising generally hydrochloric acid and metals.

Oneessential feature of the present invention 86 in the case of the alkylation of normally gaseous paraflin hydrocarbons with normally gaseous olefin hydrocarbons is the utilization of sumciently low temperatures so that the ordinarily vigorous action of the general class of catalysts mentioned in catalyzing condensation reactions 5 among hydrocarbons is moderated and reactions of alkylation occur rather than simple polymerization of the olefins involved. In other words, at the selected low temperatures employed, the rate of the polymerization reactions among the olefins is reduced while the rate of the alkylation of the parafiins' by the olefins is not reduced to the same extent so that alkylation of paraflins takes place in preference to simple polymerization of the olefins involved. When more elevated temperatures are employed which may he found necessary for accomplishing the alkylation of i normally liquid parafilns or naphthenes, conditions in respect to proportiom'ng of-the reacting hydrocarbons and the amount and character of the catalyst combination may be suitablymodified.

As a basis for the present invention it has been found that combinations of hydrochloric acid and certain metals are eifective catalysts in pro- 26 moting alkylation reactions leading to the formation of derivatives of parafiins and naphthene hydrocarbons by the addition of olefins thereto. While sufficiently good results in bringing about the desired reactions may be obtained with nuso merous combinations of acids and metals, it will- .be obvious to those conversant with catalysis in its general aspects that not all'combinations will have equivalent effects-in accelerating or promoting the desired reactions. Good results have 33 ballr, nickel, tin, and lead as representing the ture or as alloys. For example, brasses.consisting of definite proportions of zinc and copper,

and bronzes containing essentially zinc, tin and copper have been found to be very efiective when Apart from the temperature range specified as preferable when alkylating normally gaseous 5o paraflins with normally gaseous olefins, those employed when reacting a given saturated hydrocarbon'with a given olefin hydrocarbon will be varied considerably and beneficial eiiects. may also be obtained by increasing the pressure which 5 has a general effect in increasing the capacity of any given apparatus which may be employed and specific eflects in causing the liquefaction of and/or solution of normally gaseous reactingcomponents so that the reactions take place in substantially liquid or mixed liquid-vapor phase.

The process of the invention is particularly ap plicable to the alkylation of propane and the butanes with their olefinic counterparts propylene and the butylenes respectively and also with ethylene. These allq'lation reactions are of particular importance in theoil industry in con- ,nection with the cracking process, the fixed gases from which ordinarily contain large quantities of 3 and 4 carbon atom hydrocarbon both olefinic and saturated. Processes are at the present time in commercial operation which either thermally or catalytically polymerize the -3 and 4 carbon a saturated but still of a high antiknock character so that the ultimate yield of light hydrocarbon liquids from cracked gas mixtures such as stabilizer refluxes is considerably increased.

The features of the present invention also find I application in the alkylation of paraflin or cyclohydrocarbons or their mixtures which 1 are normalLv liquid. The temperature range pre-' viously mentioned is the one most applicable when dealing with the alkylation of propane and the butanes but in the case of other parafiins this range may be extended to include the temperatures most suitable for any given saturated hydrocarbons or mixture of saturated hydrocar bons including parafiins and naphthenes such as are present in straight run gasoline of a paraflin- The actual operation of the. process admits of some modification depending upon the normal phase of the reacting constituents and whether batch or continuous operations are employed. In a simple type of batch operation a hydrocarbon to be alkylated, such as, for example, normal or isobutane is cooled to a temperature within the approximate range specified in the presence of a metal or metals selected from the group already mentioned and its alkylation may be effected by the gradual introduction of hydrochloric acid and an olefin, such as, for example, isobutylene under the surface of the liquid which may be mechanically stirred to assure intimate contact between hydrochloric acid, metal, and reacting hydrocarbons. In another method of operation a parafiln may be mixed with a liquid olefin at a suitably low temperature, a suitable amount of hydrochloric acid catalyst added and the reactions of allrylation induced by a sufficiently long contact with metals. Alkylation may be allowed to progress to different stages of replacement. In the case of the alkylation of propane or butanes with propylene or the butylenes, the best products from the standpoint of motor fuel usually are produced by the condensation of equimolecular quantities. After a batch 6 treatment is completed the upper hydrocarbon layer may be removed by decantation or mechanical filtration and subjected to fractionation for the removal of uncombined hydrocarbons as a light overhead and the recovery of an intermediate motor fuel fraction.

In continuous operation a liquid mixture of parafiins and olefins containing dispersed therein the requisite amount of hydrochloric acid and cooled to a suitably low temperature may be pumped through a tubular heater containing finely divided or granular metals, the desired alkylation reactions taking place during'passage through the heater and the fractionation of the product being accomplished in succeeding fractionating equipment. The details of continuous processes of this general character are more or less familiar to those skilled in commercial operations and any necessary additions to or modifications of the general procedures will be more or less obvious, and can be made without departing from the general scope of the invention.

While thepresent process possesses particular advantages in connection with the utilization of the gases produced in oil cracking plants, it has a broader significance and includes generally the interaction of any olefin and any paraflin or' mixtures thereof at temperatures at which alkylation reactions are fostered by the preferred catalyst combinations in preference to the simple polymerization of the olefins. Y

The following example is given as illustrative of the type of results normally obtainable by the use of the present process, although it is not given with the intention of limiting the generally broad scope of the invention.

50 parts by weight of n-butane were alkylated by 45 parts of propylene. The butane was cooled to a temperature of -25 C. and 10-15 parts by weight of zinc powder were added and main- 6 tained in suspension by an eificient stirring device. During vigorous agitation a. cooled stream of propylene was introduced along with a small amount of hydrochloric acid to accomplish the alklation. The proplene was added at such a rate a that it was substantially completely absorbed. After the requisite amount had been passed into the acid-oil mixture the stirring was stopped and the aqueous-acid layer allowed to settle. The upper hydrocarbon layer was then found to consist of 85 parts by weight of hydrocarbon product which was paraflinic as indicated by its non-reactivity with potassium permanganate solution and nitrating mixture. This hydrocarbon layer was principally a mixture of heptanes of an isomeric character along with some lower molecular weight products. The octane number by the C. F. R. motor method was found to be 83.

The broad scope of the present invention is evident from the preceding specification and the results obtainable by its use in practice are evident 7 from the examples given although neither section is intended to be unduly limiting.

I claim as my invention:

1; A process for the production of octanes which. comprises subjecting butanes at temperatures of the order of to +20 C. to treatment with butenes in the presence of hydroparaflin hydrocarbons which comprises reacting a paraflin with an olefin under alkylating conditions and in the presence of hydrochloric acid and a metal above hydrogen in the electrochem- 6 ical series selected from the group consisting of aluminum, zinc, manganese, chromium, iron.

acadmium, cobalt, nickel, tin and'lead.

3. The process as defined in claim 2 further characterized in that said parailin is a straightchain paramn.

4. The process as defined in claim 2 further characterized in that said paraflin is a butane.

' 5. A process for producing alkyl derivatives of parafiin hydrocarbons which comprises reacting a parafiin with an olefin at a temperature of the order of 50 to +20 C. and in the presence ofhydrochloric acid and a metal above hydrogen in the electrochemical series selected from the group consisting of aluminum, zinc, manganese, chromium, iron, cadmium, cobalt, nickel, tin and lead.

6. A process for producing hydrocarbons boiling within the gasoline range which comprises reacting a normally gaseous parafiln with a'normally gaseous olefin under alkylating conditions and in the presence of hydrochloric acid and a metal above hydrogen in the electrochemical series selected from the group consisting of aluminum, zinc, manganese, chromium, iron, cadmium, cobalt, nickel, tin and lead.

7. A process for producing hydrocarbons boil= ing within the gasoline range which comprises reacting a normally gaseous parafiin with a normally'gaseous olefin at a temperature of the order of 50 to +20 C. and in the presence of hydrochloric acid and a metal above hydrogen in the electrochemical series selected from the group consisting of aluminum, zinc, manganese, chromium, iron, cadmium, cobalt, nickel, tin and lead.

8. A process for producing alkyl derivatives of paramn hydrocarbons which comprises reacting a'paraflin with an olefin under alkylating conditions' and in the presence of .hydrochloric acid and zinc.

9. The process as'defined in claim 8 further characterized in that said parafiin is a straightchain paramn.

10. The process as defined in claim 8 further characterized in that saidparaflin is a butane.

11. A process for producing hydrocarbons boiling within the gasoline range which comprises reacting a normally gaseous paraflin witha normally gaseous olefin under alkylating conditions and in the presence of hydrochloric acid and zinc.

12. A process for producing hydrocarbons boiling within the gasoline range which comprises reacting a normally gaseous parafiin with a normally gaseous olefin at a temperature oi'the order of 50 to +20 C. and in the presence of hydrochloric acid'and zinc.

JACQUE c. MORRELL. 

